Organic polymers for bottom antireflective coating, process for preparing the same, and compositions containing the same

ABSTRACT

A bottom antireflective coating layer is made from the compositions of organic photosensitive materials containing isoflavone chromophore by photolithography utilizing deep ultraviolet light source for producing a submicro-level, large-scale integrated chip. A copolymer being contained an isoflavone chromophore is used as a bottom antireflective coating layer for fabricating a 64-megabit or gigabit DRAMs. The antireflective coating layer enables not only to suppress reflection of light that occurs under the substrate layer but also to remove standing waves. Consequently, a high-resolution sub-micron of 100˜200 nm integrated circuit is able to be stably formed. Therefore, it is possible to increase the production of semiconductors.

FIELD OF THE INVENTION

[0001] The present invention is related to a bottom antireflective coating layer for suppressing a reflective notching that occurs at a substrate surface under a photoresist during an exposing process of photolithography using a deep ultraviolet light source to form a submicron-level, large-scale semiconductor integrated circuit and eliminating an effect of standing wave that occurs due to a variation of thickness of photoresist and using light source. More particularly, it is related to the compositions of antireflective coating materials containing an isoflavone chromophore and to a method of producing the compositions.

BACKGROUND OF THE INVENTION

[0002] An organic antireflective coating (ARC) layer is a very thin film of light absorbing material being used in photolithography for stably forming a submicron pattern of 100 nm˜200 nm or less that is essential to produce a giga-bit level, large-scale integrated chips. This thin film is called as a bottom antireflective coating (BARC or bottom ARC) because it is coated primarily on a substrate surface under the photoresist for exposing process of deep ultraviolet light.

[0003] In a conventional photolithography, there are problems of reflective notching being occurred at a substrate surface under a photoresist during an exposing process and an effect of standing wave being occurred due to a variation of thickness of photoresist and using light source. Due to those problems, it is hard to stably form a submicron pattern of 100 nm˜200 nm or less on the substrate surface. Therefore, an organic bottom ARC layer is needed for absorbing incident light having a specific wavelength.

[0004] The ARC layer must have an excellent property of light absorption as the wavelength of light source is shortened (G-line, I-line, KrF, ArF, F₂ etc.) in accordance with the technology of submicron-level, large-scale integrated chip is advanced [M. Padmanaban et al., Proc. SPIE, 3678, 550 (1999); E. Iguchi et al., Proc. SPIE, 3999, 521 (2000); M. Padmanaban et al., Proc. SPIE, 3333, 206 (1998)]

[0005] Even a variety of techniques have remarkably been developed in the semiconductor manufacturing industry, the conventional photolithography being spin coated a photoresist on a silicone substrate for a subsequent exposure process becomes no more suitable to apply for stably producing a sub-micron pattern of 100˜200 nm. Consequently, a special technique of thin film coating is essentially needed prior to coating a photoresist. The antireflective coating layer in the photolithography becomes indispensable for preventing an effect of standing wave in the photoresist occurred from interference between an incident light to photoresist and the reflected light from the substrate surface. It will also prevent or remarkably reduce the reflections caused from the topography of already-formed circuits and the reflective notching on the edges. Therefore, a desired critical dimension (CD) of submicron circuit could be accurately controlled. It also eases the tolerance conditions for producing process.

[0006] This antireflective coating layer could be divided into an organic material being spin-coated according to its compositions and an inorganic material being coated by chemical vapor deposition. In the recent year, an organic antireflective coating is increasingly used.

[0007] Particularly, due to an advanced exposure process used in a high energy short wavelength such as the deep ultraviolet light, a chromophore having a high light absorption in the deep ultraviolet light spectrum is required, mainly leading the development of organic antireflection coating layer using the naphthalene or anthracene derivatives. [J. Fahey et al., Proc. SPIE, 2195, 422 (1994); K. Mizutani et al., Porc. SPIE. 3678, 518 (1999)]. This technique is disclosed in the U.S. Pat. Nos. 5,693,692, 5,851,738, 5,919,599 and 6,033,830.

SUMMARY OF THE INVENTION

[0008] A technological object of the present invention is to provide a novel organic photosensitive material containing an isoflavone chromophore and a method for producing the same, which enable to use as an antireflective coating layer in a photolithographic process using a Krytonfluoride (KrF) eximer laser of 248 nm-wavelength and Argonfluoride (ArF) eximer laser of 193 nm-wavelength as an exposing light source for producing a large-scale integrated semiconductor device.

[0009] Another object of the present invention is to provide the organic polymer material having an isoflavone chromophore as a side chain for preventing light reflections that are transmitted through the photoresist during a light exposing process and a method for producing the same.

[0010] Other object of the present invention is to provide the compositions of bottom antireflective coating layer using the organic polymer materials.

[0011] Still other object of the present invention is to provide a protective coating layer produced by using the compositions of bottom antireflective coating layer and a method for producing the same.

DETAILED DESCRIPTION OF THE INVENTION

[0012] Generally, an incident light is transmitted, absorbed, reflected or refracted depending on the optical property of materials and encountered interfaces. By utilizing this well known property of light, the present invention is developed an organic antireflective coating (ARC) layer for absorbing the incident light. If an organic ARC layer has the same refractive index as the photoresist has, there would be no reflections at an interface of photoresist and ARC layer. For this reason, the ARC layer must have the same optical property with a commercial DUV photoresist to have identical performance of lithographic. Consequently, the organic antireflective coating (ARC) layer of the present invention is designed for absorbing the incident light so that the penetrated light thru the interface of photoresist and ARC layer will be absorbed before reaching the substrate surface.

[0013] Therefore, the organic bottom ARC layer should have an excellent property of high light absorption against a specific exposure wavelength of 248 nm, 193 nm and 157 nm of eximer laser for photolithographic process.

[0014] Along the propagation of photolithographic process that is using a Krytonfluoride (KrF) eximer laser, the role of antireflective coating layer becomes more important matter. Therefore, most compositions of organic antireflective layer are required to have following conditions:

[0015] It must have a proper optical constant such as a refractive index (n) and extinction coefficient (k) for a light source, which is used in a semiconductor production.

[0016] The organic bottom antireflective coating layer should have a high selection ratio with respect to plasma dry etching compared with an upper layer of photoresist and should not have defects in accordance with dry etching.

[0017] It must not have a phenomenon of intermixing the photoresist with bottom antireflective coating layer, and have a reactive site for the sake of forming an appropriate crosslink in the organic polymer.

[0018] The organic bottom antireflective coating layer should be in acid equilibrium with photoresist after exposing and developing process so as not to occur undercutting or footing at a sublayer of pattern.

[0019] It must have capability of layer formation and layer uniformity for forming a proper thickness of bottom antireflective coating layer suitable to process revolution per minute (RPM).

[0020] A polymer for a bottom antireflective coating (BARC) layer of the present invention comprises isoflavone chromophore having a high light absorption at 248 nm and 193 nm of exposure wavelengths in a main chain, monomer contained a hydroxyl group for crosslinking during a formation of antireflective coating layer, co-monomer for adjusting the property of polymer and co-polymer, ter-polymer or quarto-polymer comprised with three or four different kinds of monomers. A general formula of polymer is represented as follows:

[0021] That is, a polymer of the present invention for bottom antireflective coating layer has a structure -(Ma)_(k)-(M_(b))_(l)-(M_(c))_(m)-(M_(d))_(n)-. Among them,

[0022] M_(a) is an (meth) acrylate monomer containing an isoflavone chromophore, being represented by the above Formula (1).

[0023] M_(b) is an (meth) acrylate monomer containing a hydroxyl group, which is represented by the above Formula (2).

[0024] M_(c) is an alkylmaleimide monomer containing hydroxyl group, which is represented by the above Formula (3).

[0025] And M_(d) is (meth) acrylate monomer, represented by the above Formula (4).

[0026] In the above Formulas (1), (2), (3) and (4), R₁˜R₇ independently represent each of hydrogen, methoxy, hydroxy, halogen, aldehyde. C₁˜C₆ represent alkoxyalkyl or C₁˜C₅ represent alkoxyalkane. R₈, R₉ and R₁₀ represent hydrogen or methyl group, and R₁₁ and x represent C₁˜C₆ alkyl group.

[0027] In the General Formula I, the values of mol ratio are k, 0.1˜0.5, l and m, 0.0˜0.4 and n, 0.3˜0.6 based on the total molar feed ratio of k+l+m+n.

[0028] The isoflavone chromophore monomer (1) of the present invention has excellent property of plasma etching compared with the conventional anthracene group chromophore derivative. It has not only a high light absorption at 248 nm wavelength spectrum of Krytonfluoride (KrF) eximer laser, but also enhanced adhesion on a wafer due to the substitution of hydrophilic moiety.

[0029] The polymer of General Formula I of the present invention could be produced by reacting a radical initiator for 2 to 24 hours under an inert gas environment such as a Nitrogen or Argon. The radical initiators commonly used are thermal decomposition initiators such as a benzoil peroxide (BPO), 2,2′-azobisisobutyronitrile (AIBN) and Di-tert-butyl peroxide (DTBP). If one of these radical initiators is used, a reaction would be performed at the temperature of 50°˜90° C. A solvent such as a dioxane, tetrahydrofuran and benzene is popularly used for a polymerizing solvent. Therefore, it is possible to synthesize a polymer having a proper molecular weight with etching performance by adjusting each amount of monomer, polymerizing solvent or radical initiator. The molecular weight of polymer of General Formula I should be within a range of 5,000 to 100,000 g/mol measured by a gel-permeation chromatography (GPC). The range of molecular weight of polymer could be adjusted for proper coating capability by varying the synthesizing conditions.

[0030] The composition of organic bottom antireflective coating (BARC) material is produced through the following process: 0.5˜50 weight % of polymer of the General Formula I is added to an organic solvent having an excellent coating layer forming capability, such as a propyleneglycol monomethylether acetate (PGMEA), ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and cyclohexanone being used for manufacturing semiconductor device. Then, the solution is dissolved by adding various functional additives. Next, the solution is filtered and coated on a silicon wafer to form a bottom ARC film layer. Then, the coated silicon wafer is hard-baked to bring crosslinking at a proper temperature.

[0031] By applying this antireflective coating layer, the problems due to the reflections in a photolithographic process using deep ultraviolet could be entirely controlled so that the production of semiconductor devices is facilely performed.

[0032] According to the present invention, the polymer of antireflective coating layer being contained isoflavone chromophore reveals an excellent lithographic performance as an organic bottom antireflective coating layer in 248 nm, 193 nm and 157 nm of light exposure wavelength. The present polymer is verified as a useful material for forming a submicron circuit of semiconductor chips due to fast plasma etching speed being compared with the conventional antireflective coating layer formed based on anthracene chromophore.

Implementing Example

[0033] Hereinafter, according to the present invention, a producing method of methacrylic monomer and methacrylic polymer contained an isoflavone chromophore, the compositions of organic bottom antireflective coating layer being applied methacrylic monomer and methacrylic polymer and the producing method are specifically described in a detail accompanying with implementing examples. However, a purpose of implementing examples is for explaining the present invention, but not limited to the implementing examples.

EXAMPLE 1 Synthesizing Isoflavonyl Methacylate as a Chromophore Monomer (IFVMA)

[0034]

[0035] Dissolve 7-hydroxyisoflavone (5)(100.00 g, 0.42 mol) into pyridine (150 ml) and stir for five hours at the temperature of 4° C. by gradually adding methacryloyl chloride (42.00 g, 0.42 mol). After precipitating reactant in the cold water and filtering, extract the filtered reactant several times with methylene chloride, and refining. Then, dry the product in a vacuum for recovering a light yellowish crystalline of isoflavonyl methacrylate (6). Yield: 116.4 g (82%). Melting point: 168° C.

EXAMPLE 2 Synthesizing Isoflavonyl Methacrylate Monomer (MIFVMA) Contained Methoxy Group

[0036]

[0037] Dissolve formononetin (7)(100.00 g, 0.37 mol) into pyridine (150 ml) and stir the solution for 3 hours at temperature of 4° C. by gradually adding methacryloyl chloride (37.00 g, 0.37 mol). After precipitating reactant in the cold water and filtering, extract the filtered reactant several times with chloroform and refining. Then, dry the product in a vacuum to recover a deep yellowish crystalline of isoflavonyl methacrylate (8) having methoxy group. Yield: 119.2 g (87%) Melting point: 194° C.

EXAMPLE 3 Synthesizing Terpolymer Using Monomer (2), (4) and (6)

[0038] In a polymerizing container, Isoflavonyl Methacylate (IFVMA) (6) (20.00 g, 65.5 mmol), hydroxyethymethacrylate (HEMA) (2) (8.52 g, 65.5 mmol), methylmethacrylate (MMA) (4) (8.74 g, 87.3 mmol) and 5-mol % of AIBN are placed and dissolved with dioxane (70 ml). Then, the solution is polymerized for 10 hours at the temperature of 60° C. under a nitrogen environment. After precipitating reactant in a sufficient methanol, the filtering and drying process are performed thru for synthesizing terpolymer of poly (IFVMA-HEMA-MMA). A yield of poly (IFVMA-HEMA-MMA) is 83%. A weight average molecular weight being measured by GPC is about 46,000 g/mol so as to easily form a film layer.

EXAMPLE 4 Synthesizing Terpolymer Using Monomer (2), (4) and (8)

[0039] In a synthesizing container, methoxy substituted Isoflavonyl Methacrylate (MIFVMA)(8)(22.00 g, 65.4 mmol), hydroxyethylmethacrylate (HEMA)(2)(98.52 g, 65.5 mmol), methymethacrylate (MMA)(4)(8.74 g, 87.3 mmol) and 5-mol % of AIBN are placed and dissolved with tetrahydrofuran (79 ml). The solution is polymerized for 10 hours at the temperature of 60° C. under a nitrogen environment. After precipitating reactant in a sufficient methanol, the filtering and drying process are performed for synthesizing terpolymer of poly (MIFVMA-HEMA-MMA). A yield of poly (MIFVMA-HEMA-MMA) is 91%. A weight average molecular weight measured by GPC is approximately 44,000 g/mol so as to easily form a film layer.

EXAMPLE 5 Synthesizing Quatropolymer Using Monomer (2), (3), (4) and (6)

[0040] In a polymerizing container, Isoflavonyl Methacylate (IFVMA)(6) (9.00 g, 38 mmol), hydroxyethylmaleimide (HOEMI) (3) (5.36 g, 38 mmol), hydroxyethylmethacrylate (HEMA) (2) (8.52 g, 65.5 mmol), methymethacrylate (MMA) (4) (8.74 g, 87.3 mmol) and 5-mol % of AIBN are placed and dissolved with a mixed solvent of tetrahydrofuran and methylethylketone (73 ml). The solution is polymerized for 10 hours at the temperature of 60° C. under a nitrogen environment. After precipitating reactant in a sufficient methanol, the filtering and drying process are performed for synthesizing quatropolymer of poly (IFVMA-HOEMI-HEMA-MMA). A yield of poly (IFVMA-HOEMI-HEMA-MMA) is 79%. A weight average molecular weight being measured by GPC is about 40,500 g/mol so as to easily form a film layer.

EXAMPLE 6 Synthesizing Quatropolymer Using Monomer (2), (4), (6) and (8)

[0041] In a polymerizing container, IFVMA Monomer (6) (9.00 g, 38 mmol), MIFVMA Monomer (8) (10.3 g, 38 mmol), hydroxyethylmethacrylate (2) (HEMA) (8.52 g. 65.5 mmol), methylmethacrylate (MMA) (4) (8.74 g, 87.3 mmol) and 5 mol % of AIBN are placed and dissolved with a mixed solvent of tetrahydrofuran and methylethylketone (73 ml). Then, the solution is polymerized for 10 hours at the temperature of 60° C. in a nitrogen environment. After precipitating reactant in a sufficient methanol, the filtering and drying process are performed for synthesizing quatropolymer of poly (IFVMA-MIFVMA-HEMA-MMA). A yield of poly (IFVMA-MIFVMA-HEMA-MMA) is 88%. A weight average molecular weight being measured by GPC is approximately 43,500 g/mol so as to easily form a film layer.

EXAMPLE 7 Producing and Applying the Compositions of Organic Bottom Antireflective Coating Layer

[0042] One of polymers being obtained in the above examples 1 thru 6 is dissolved in propylene glycol monomethylether acetate with a weight ratio of 1:20˜1:50. Stir the solution after adding various additives such as an acid-catalyzed thermo-crosslinker and stabilizer. The solution is filtered through a 0.05 μm of membrane filter to produce an organic solution of antireflective coating layer. This organic solution is spin-coated on a silicon wafer and crosslinked for 10 to 120 seconds at the temperature of 100° C.˜250° C. to prevent intermixing with a photoresist. Hereinafter, following a general producing process, a photolithographic process for submicron circuit is performed by spin coating a commercial photoresist on the antireflective coating layer. The compositions of organic bottom antireflective coating layer being applied the polymers, which is obtained from implementing examples, are in acid equilibrium with photoresist after the light exposing process during a development. Consequently, there is no undercutting or footing formed at the sublayer pattern of photoresist. A dimensional variation in a submicron pattern due to reflective notching is so negligible that the formation of submicron circuit is stably performed.

[0043] As disclosed throughout the implementing examples, because the antireflective coating layer being used polymer having basic structure of terpolymer or quartopolymer adapts a covalent bond of side chain having a high light-absorptive isoflavone chromophore, the ARC layer has excellent heat stability without generating gases during a high heat exposure process. The ARC layer of the present invention also has not only a capability of sufficient light absorption to be qualified a bottom antireflective coating layer, but also a capability of suppressing reflections of light that occurs underneath the substrate layer during an exposure process and eliminating the standing waves that occurs due to the thickness variation of photoresist and using light source. Due to a high etching capability with respect to plasma, it enables to stably photo-transmit a clear image of submicron circuit on the substrate surface

[0044] Accordingly, when a copolymer of the present invention is applied to an exposure process of bottom antireflective coating layer, which is used 248 nm, 193 nm or 157 nm of exposure wavelength of eximer laser, a formation of submicron pattern for an integrated circuit system having a 64-mega bit DRAM or higher memory device of Giga bit or 0.1˜0.2 micron level pattern is stably performed. Consequently, the production rate of semiconductor devices could be remarkably increased.

[0045] While the present invention has been described in detail with its preferred embodiments, it will be understood that it further modifications are possible. The present application is therefore intended to cover any variations, uses or adaptations of the invention following the general principles thereof, and includes such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains within the limits of the appended claims. 

What is claimed is:
 1. A monomer of isoflavonyl derivative is one component of polymer being applied to a semiconductor photolithographic process using 248 nm, 193 nm or 157 nm of exposure wavelength of eximer laser as an exposing light source for an antireflective coating layer, a chemical formula of said monomer represents as follows:

wherein, R₁˜R₇ represent independently hydrogen, methoxy, hydroxy, halogen, aldehyde, C₁˜C₆ represent alkoxyalkyl, or C₁˜C₅ represent alkoxyalkane, and R₈ represents hydrogen or methyl group.
 2. A binder polymer has repeating units in a main chain including co- to quatro-, a structural formula of said binder polymer represents as below:

wherein, R₁˜R₇ independently represent hydrogen, methoxy, hydroxy, halogen, aldehyde, C₁˜C₆ represent alkoxyalkyl or C₁˜C₅ represent alkoxyalkane, p1 R₈, R₉ and R₁₀ represent hydrogen or methyl group, R₁₁ and x represent C₁˜C₆ alkyl group, and mol ratio of each monomer is that k is 0.1˜0.5, l and m are 0.0˜0.4 and n is 0.3˜0.6 based on a total molar feed ratio of component k+l+m+n.
 3. The binder polymer of claim 3, wherein a weight average molecular weight of said polymer is in a range of 10,000˜100,000 g/mol.
 4. A composition of bottom antireflective coating material for processing semiconductor comprises: binder polymer represented by a following structural formula,

alkylated aminoplast crosslinker, an active or latent protonic acid catalyst for curing, and a low-to-medium boiling point alcohol-containing solvent, wherein, R₁˜R₇ independently represent hydrogen, methoxy, hydroxy, halogen, aldehyde, C₁˜C₆ represent alkoxyalkyl or C₁˜C₅ represent alkoxyalkane, R₈, R₉ and R₁₀ represent hydrogen or methyl group, R₁₁ and x represent C₁˜C₆ alkyl group, and mol ratio of each monomer is that k is 0.1˜0.5, l and m are 0.0˜0.4 and n is 0.3˜0.6 based on a total molar feed ratio of component k+l+m+n.
 5. A semiconductor device containing a bottom antireflective coating material for using semiconductor fabrication, a structural formula of said semiconductor device represents:

wherein, said bottom antireflective coating material is made of a binder polymer an acid catalyzed crosslinker and a low-to-medium boiling point alcohol-containing solvent, and wherein, R₁˜R₇ independently represent hydrogen, methoxy, hydroxy, halogen, aldehyde, C₁˜C₆ represent alkoxyalkyl or C₁˜C₅ represent alkoxyalkane, R₈, R₉ and R₁₀ represent hydrogen or methyl group, R₁₁ and x represent C₁˜C₆ alkyl group, and mol ratio of each monomer is that k is 0.1˜0.5, l and m are 0.0˜0.4 and n is 0.3˜0.6 based on a total molar feed ratio of component k+l+m+n.
 6. A method for synthesizing an isoflavonyl methyl (meth) acrylate represented by a following chemical formula comprises steps of:

dissolving 7-hydroxyisoflavone derivatives into pyridine, stirring solution for two to seven hours at temperature of 4° C. by gradually adding methacryloyl chloride, extracting filtered reactant several times with organic solvent, refining extracted reactant, and drying product in a vacuum for recovering isoflavonyl methacrylate.
 7. A method for synthesizing a binder polymer having repeating units in a main chain, including co- to quatro-, with a solution comprising a polymerization solvent selected from a group of dioxane, tetrahydrofuran, methylethylketone or aromatic solvent and a radical initiator selected from a group of benzoil peroxide (BPO), 2,2′-azobisisobutyronitrile (AIBN) or Di-tert-butyl peroxide (DTBP), and represented by a following structural formula, comprises steps of:

dissolving monomer being selected from a group of substituted or unsubstituted isoflavone chromophore monomer, hydroxyalkylmaleimide monomer, hydroxyalkylmethacrylate monomer, alkylmethacrylate monomer and 1˜10 mol % of radical initiator with a solvent, polymerizing for 2˜10 hours at temperature of 60° C. in a nitrogen environment, filtering and drying for synthesizing binder polymer, wherein, R₁˜R₇ independently represent hydrogen, methoxy, hydroxy, halogen, aldehyde, C₁˜C₆ represent alkoxyalkyl or C₁˜C₅ represent alkoxyalkane, R₈, R₉ and R₁₀ represent hydrogen or methyl group, R₁₁ and x represent C₁˜C₆ alkyl group, and mol ratio of each monomer is that k is 0.1˜0.5, l and m are 0.0˜0.4 and n is 0.3˜0.6 based on a total molar feed ratio of component k+l+m+n.
 8. A method for producing an antireflective coating layer containing a binder polymer represented by a following structural formula comprises steps of:

dissolving said polymer in a solvent being selected from a group consisting of propyleneglycol monomethylether acetate (PGMEA), ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and cyclohexanone; spin-coating a solution on a silicone wafer; baking at from about 110° C. to 250° C. for 30 to 120 seconds; and over-coating a photoresist; wherein, R₁˜R₇ independently represent hydrogen, methoxy, hydroxy, halogen, aldehyde, C₁˜C₆ represent alkoxyalkyl or C₁˜C₅ represent alkoxyalkane, R₈, R₉ and R₁₀ represent hydrogen or methyl group, R₁₁ and x represent C₁˜C₆ alkyl group, and mol ratio of each monomer is that k is 0.1˜0.5, l and m are 0.0˜0.4 and n is 0.3˜0.6 based on a total molar feed ratio of component k+l+m+n. 